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Thermodynamics of the Under-Potential Deposition of Hydrogen on Polycrystalline Platinum in Aqueous Trifluoromethanesulfonic Acid Solution

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Abstract

Understanding of the electrocatalytic behavior of the Pt/Nafion® ionomer interface is of great importance to fuel cell technology. Trifluoromethanesulfonic acid (CF3SO3H) is used as an electrolyte because it is the smallest fluorinated sulfonic acid and serves as a suitable molecular model mimicking the Nafion® ionomer. The under-potential deposition of H (UPD H) on polycrystalline Pt electrode in CF3SO3H is investigated using cyclic voltammetry in the 278–333 K temperature (T) range. The general electrochemical adsorption isotherm is used to determine the Gibbs energy (−13 ≤ Δ ec − ads G°(HUPD) ≤ −27 kJ mol−1), entropy (−59 ≤ Δ ec − ads S°(HUPD) ≤ +20 J mol−1 K−1), and enthalpy (−8 ≤ Δ ec − ads H°(HUPD) ≤ −43 kJ mol−1) of electro-adsorption, and the Pt–HUPD surface bond energy (+225 ≤ \( {E}_{\mathrm{Pt}-{\mathrm{H}}_{\mathrm{UPD}}} \) ≤ +261 kJ mol−1). The lateral interactions between the HUPD adatoms are repulsive; the energy of lateral interactions is T-dependent (ω(HUPD) = a − b T) and is in the +14 ≤ ω(HUPD) ≤ +22 kJ mol−1 range. The values of Δ ec − ads G°(HUPD), Δ ec − ads S°(HUPD), Δ ec − ads H°(HUPD), and \( {E}_{\mathrm{Pt}-{\mathrm{H}}_{\mathrm{UPD}}} \) for UPD H in CF3SO3H are very similar to the analogous values obtained in aqueous H2SO4 and HClO4 solutions. The anion present in the electrolyte has a small impact on UPD H and influences the values of Δ ec − ads G°(HUPD) only over a narrow HUPD coverage range. The anion nature has practically no impact on the values of Δ ec − ads S°(HUPD), Δ ec − ads H°(HUPD), or \( {E}_{\mathrm{Pt}-{\mathrm{H}}_{\mathrm{UPD}}} \).

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Authors and Affiliations

  1. Nissan Research Center, Nissan Motor Co., Ltd., 1-Natsushima Cho, Yokosuka, Kanagawa, 237-8523, Japan

    Yoshihisa Furuya

  2. Nissan Motor Company Co. LTD., 1-Natsushima Cho, Yokosuka, Kanagawa, 237-8523, Japan

    Tetsuya Mashio & Atsushi Ohma

  3. Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, ON, K7L 3N6, Canada

    Yoshihisa Furuya & Gregory Jerkiewicz

Authors
  1. Yoshihisa Furuya
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  2. Tetsuya Mashio
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  3. Atsushi Ohma
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  4. Gregory Jerkiewicz
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Correspondence to Gregory Jerkiewicz.

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Furuya, Y., Mashio, T., Ohma, A. et al. Thermodynamics of the Under-Potential Deposition of Hydrogen on Polycrystalline Platinum in Aqueous Trifluoromethanesulfonic Acid Solution. Electrocatalysis 6, 109–116 (2015). https://doi.org/10.1007/s12678-014-0227-9

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  • DOI: https://doi.org/10.1007/s12678-014-0227-9

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